Copper, cobalt, nickel and iron complexes of disazo dyes

ABSTRACT

Compounds which in the form of the free acid are of the general formula I ##STR1## where A is a radical of the formula ##STR2## the radicals Y independently of one another are each hydroxyl or amino, X is hydrogen, hydroxysulfonyl or a radical of the formula 
     
         D--N═N--, 
    
     R is a radical of 1-aminonaphthalene-4-, -5-, -6-, -7- or -8-monosulfonic acid or of 1-aminonaphthalene-3,6-, -3,7-, -3,8-, -4,7-, or -4,8-disulfonic acid, or a Cu, Fe, Ni, Co, Mn or Cr complex thereof, and D is phenyl which is unsubstituted or substituted by methyl, methoxy, ethoxy, nitro, chlorine, bromine or sulfo, or is sulfo-substituted naphthyl. These compounds are preferably used for dyeing leather.

The present invention relates to compounds which in the form of the free acids are of the general formula ##STR3## where A is a radical of the formula ##STR4## the radicals Y independently of one another are each hydroxyl or amino, X is hydrogen, hydroxysulfonyl or a radical of the formula

    D--N═N--,

R is a radical of 1-aminonaphthalene-4-, -5-, -6-, -7- or -8-monosulfonic acid or of 1-aminonaphthalene-3,6-, -3,7-, -3,8-, -4,7- or -4,8-disulfonic acid, or a Cu, Fe, Ni, Co, Mn or Cr complex thereof, and D is phenyl which is unsubstituted or substituted by methyl, methoxy, ethoxy, nitro, chlorine, bromine or sulfo, or is sulfo-substituted naphthyl.

The compounds of the formula I can be prepared by reacting a compound of the formula ##STR5## with a diazo compound of an amine of the formula

    R--NH.sub.2

and, if desired, converting the coupling product to a metal complex. The reactions are known in principle, and do not possess any special features compared with the preparation of known substances.

R is particularly preferably 4-, 6- or 8-sulfonaphthyl or the Fe complex.

Furthermore, Y is preferably hydroxyl and X is preferably hydrogen, and preferred dye mixtures are those containing a compound in which X is H with about 5-20% of a compound in which X is D--N═N--.

The compounds of the formula I are particularly useful for dyeing leathers, such as those retanned with vegetable or synthetic tanning agents. Fast brown dyeings are obtained.

In the Examples which follow, parts and percentages are by weight, unless stated otherwise.

EXAMPLE 1

19.9 parts of 1-amino-2-hydroxy-3,5-dinitrobenzene are diazotized in a conventional manner, and the product is coupled to 11 parts of resorcinol in a solution rendered alkaline with sodium carbonate. The diazonium salt obtained from 22.3 parts of 1-aminonaphthalene-4-sulfonic acid is then added to the suspension, at pH 8-9. After coupling is complete, the reaction mixture is brought to pH 5 with acetic acid, 38 parts of anhydrous iron(III) chloride are added, and the mixture is heated at 90°-95° C. for about 3 hours, at pH 4-5.

When metallization is complete, the dye is precipitated by the addition of sodium chloride, isolated and dried. The iron complex of the compound of the formula ##STR6## dyes leather in lightfast and wetfast yellowish brown hues.

The dyes listed in the Table below can be synthesized by the above method.

    __________________________________________________________________________      ##STR7##                                                                                        Hue of the dyeing on leather, obtained                       Ex-               with the metal complex                                       ample                                                                              R             Cu   Cr   Co   Ni   Fe                                       __________________________________________________________________________          ##STR8##     reddish- brown      yellowish- brown                         3                                                                                   ##STR9##          reddish- brown yellowish- brown                         4                                                                                   ##STR10##                   reddish- brown                                5                                                                                   ##STR11##    reddish- brown                                               6                                                                                   ##STR12##                        yellowish- brown                         7                                                                                   ##STR13##              reddish- brown                                     8                                                                                   ##STR14##    reddish- brown      yellowish- brown                         9                                                                                   ##STR15##         reddish- brown                                                                           reddish- brown                                                                      yellowish- brown                         10                                                                                  ##STR16##              reddish- brown                                     __________________________________________________________________________

EXAMPLE 11

19.9 parts of 1-amino-2-hydroxy-3,5-dinitrobenzene are diazotized in a conventional manner, and the product is coupled to 11 parts of resorcinol in a solution rendered alkaline with sodium carbonate. The diazonium salt obtained from 22.3 parts of 1-aminonaphthalene-4-sulfonic acid is then added to the suspension, at pH 8-9. After formation of the diazo dye is complete, the diazo compound obtained from 21.8 parts of 1-amino-2-sulfo-4-nitrobenzene is added in such a manner that coupling takes place at a pH of from 6 to 7. When coupling is complete, the reaction mixture is brought to pH 5 with acetic acid, and complexing with anhydrous iron(III) chloride is carried out by a procedure similar to that described in Example 1.

When metallization is complete, the dye is precipitated by the addition of sodium chloride, isolated and dried. The iron complex of the compound of the formula ##STR17## gives lightfast and wetfast brown dyeings on chrome side leather retanned with vegetable or synthetic tanning agents.

The dyes listed in the Table below can be prepared by the above method.

    ______________________________________                                          ##STR18##                                                                                                     Hue of the                                     Ex-                             Fe complex                                     ample R            X            on leather                                     ______________________________________                                         12                                                                                    ##STR19##                                                                                   ##STR20##   yellowish-brown                                13                                                                                    ##STR21##                                                                                   ##STR22##   brown                                          14                                                                                    ##STR23##                                                                                   ##STR24##   yellowish-brown                                15                                                                                    ##STR25##                                                                                   ##STR26##   brown                                          16                                                                                    ##STR27##                                                                                   ##STR28##   reddish-brown                                  17                                                                                    ##STR29##                                                                                   ##STR30##   brown                                          18                                                                                    ##STR31##                                                                                   ##STR32##   brown                                           18a                                                                                  ##STR33##                                                                                   ##STR34##   brown                                          ______________________________________                                    

EXAMPLE 19

23.4 parts of 6-nitro-2-amino-1-phenol-4-sulfonic acid are diazotized in a conventional manner, and the product is coupled to 11 parts of resorcinol in a solution which has been rendered alkaline with sodium carbonate. The diazonium salt obtained from 22.3 parts of 1-aminonaphthalene-4-sulfonic acid is then added to the suspension, at pH 8-9. When coupling is complete, the disazo dye is complexed with iron(III) chloride by a procedure similar to that described in Example 1, and the complex is isolated.

The iron complex of the compound of the formula ##STR35## dyes leather in yellowish brown hues with good tinctorial properties.

The dyes listed in the Table below can be prepared by the method described in Example 19.

    ______________________________________                                          ##STR36##                                                                                                    Hue of the                                      Ex-                            Fe complex                                      ample A           R            on leather                                      ______________________________________                                         20                                                                                    ##STR37##                                                                                  ##STR38##   yellowish-brown                                 21                                                                                    ##STR39##                                                                                  ##STR40##   yellowish-brown                                 22                                                                                    ##STR41##                                                                                  ##STR42##   yellowish-brown                                 23                                                                                    ##STR43##                                                                                  ##STR44##   yellowish-brown                                 ______________________________________                                    

EXAMPLE 24

23.4 parts of 4-nitro-2-amino-1-phenol-6-sulfonic acid are coupled to 11 parts of resorcinol in a conventional manner, in a solution rendered alkaline with sodium carbonate. The diazonium salt obtained from 22.3 parts of 1-aminonaphthalene-4-sulfonic acid is then added to the monoazo dye, at pH 8-9. When the formation of the disazo dye is complete, the product is coupled, at pH 6-7, to the diazo compound obtained from 11.1 parts of 1-amino-2-methoxybenzene, and the dye is then complexed with iron(III) chloride by a procedure similar to that described in Example 1, and the complex is isolated.

The iron complex of the compound of the formula ##STR45## dyes leather in yellowish brown hues with good allround fastness.

The dyes listed in the Table below can be synthesized by the above method.

    ______________________________________                                          ##STR46##                                                                     Ex-                          Hue of the Fe complex on                          ample X.sub.1 X.sub.2 X.sub.3                                                                               leather                                           ______________________________________                                         29    OH      NH.sub.2                                                                               H      brown                                             30    NH.sub.2                                                                               NH.sub.2                                                                               H      brown                                             31    NH.sub.2                                                                               NH.sub.2                                                                               SO.sub.3 H                                                                            brown                                             ______________________________________                                    

    __________________________________________________________________________      ##STR47##                                                                     Ex-                                  Hue of the Fe                             ample                                                                              A          R          X          complex on leather                        __________________________________________________________________________     25                                                                                  ##STR48##                                                                                 ##STR49##                                                                                 ##STR50## brown                                     26                                                                                  ##STR51##                                                                                 ##STR52##                                                                                 ##STR53## brown                                     27                                                                                  ##STR54##                                                                                 ##STR55##                                                                                 ##STR56## brown                                     28                                                                                  ##STR57##                                                                                 ##STR58##                                                                                 ##STR59## brown                                     __________________________________________________________________________ 

What is claimed as new and desired to be secured by Letters Patent of the United States is:
 1. The complex having the formula ##STR60## 